GB2327892A - Ultra-violet curable coating - Google Patents
Ultra-violet curable coating Download PDFInfo
- Publication number
- GB2327892A GB2327892A GB9716194A GB9716194A GB2327892A GB 2327892 A GB2327892 A GB 2327892A GB 9716194 A GB9716194 A GB 9716194A GB 9716194 A GB9716194 A GB 9716194A GB 2327892 A GB2327892 A GB 2327892A
- Authority
- GB
- United Kingdom
- Prior art keywords
- coating
- substrate
- lamp
- curing zone
- lamps
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Plasma & Fusion (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A substrate is coated with a mixture including at least a reactive part. The reactive part comprises between 30% and 100% multi-functional material, and is photo-initiator free. The multifunctional material may have three or more functional acrylate groups, and the coating may also contain a pre-polymer. The coated substrate is exposed, in a curing zone, to ultra-violet light from at least one lamp which has a power output of at least 140 wats per linear centimetre. A substantially inert atmosphere is maintained in the curing zone where the substrate is exposed to the ultra-violet light.
Description
DESCRIPTION OF INVENTION "IMPROVEMENTS IN OR RELATING TO CURABLE COATING"
THE PRESENT INVENTION relates to curable coating, and more particularly relates to curable coating utilising radiation, especially radiation in the form of ultra-violet light.
It has been proposed previously to provide various coatings which can be applied to a substrate in a liquid form and which can then be cured to form a solid coating.
Typically, the liquid coating incorporates unsaturated organic compounds which include C=C double bonds. These compounds present within the liquid coating are effectively polymerised during the curing process.
It has been proposed to effect the curing utilising high energy electron radiation. Typically electrons are delivered by an electron beam accelerator which normally operates at a voltage in excess of l5OkVe, although alternatively a nuclear source may be utilised. The radiation breaks some of the C=C double bonds present in the unsaturated organic material, generating free radicals which initiate free radical polymerisation of the remaining material. The equipment necessary to carry out this process is costly to purchase and has to be specially shielded to avoid any leakage of gamma radiation.
There have been many proposals concerning coatings which can be cured, in response to ultra-violet light, involving free radical initiated polymerisation. Typically these coatings utilise a photo-initiator. A photoinitiator in this process is a material that absorbs light, and generates free radicals. The free radicals initiate the polymerisation of the coating. Photo-initiators are generally expensive, and can give rise to problems. For example, they can create an undesirable odour or taste (which may be relevant when the coating is going to be in contact with a food product) and can also cause "yellowing", which is a tendency for the cured coating to adopt a yellow colour over the course of time.
It has been proposed to provide a coating which can be cured on exposure to ultra-violet light which does not incorporate a photo-initiator. A coating of this type is disclosed in US-A-5,446,073. This Specification teaches a formulation which has a balance of "acceptor" and "donor" species. The process described in US-A-5,446,073 has not yet been adopted by industry, primarily because the reactive materials required are not readily commercially available. Also, the curing process is relatively slow with cure times typically being measured in terms of minutes. A further disadvantage of this technique is that it requires a combination of electron donating monomers and electron accepting monomers of relatively low molecular weight, and monomers in general are regarded as being prone to shrinkage during cure and are also regarded as being toxic since they may relatively easily penetrate the skin.
It has been discovered that short wavelength light may be used to effect a cure by direct fragmentation, in a similar way to the electron beam accelerator. Thus, it has been proposed to use light from excimer lamps, which have a wavelength of 172 mm, to cure radiation curable coatings without the use of a photo-initiator. However, this technique has only been used successfully with very thin coatings, typically coatings less than 1 ssm thick. The excimer energy is not able to penetrate readily into a coating which is of a greater thickness without excessive heat being generated. If an excimer lamp were used to irradiate a 10 ssm thick coating, it would produce a "cured skin" on the surface, but not a complete cure.
The present invention seeks to provide a W cured coating in which the disadvantages of prior proposals are obviated or reduced.
According to one aspect of the present invention, there is provided a method of coating a substrate, the method comprising the steps of applying a coating composition to at least selected areas of the substrate, exposing the coated substrate to ultra-violet light from at least one lamp having a power output of at least 140 watts per linear centimetre in a curing zone, to initiate curing of the coating, the coating composition comprising a mixture including at least a reactive part comprising between 30% and 100% multi-functional material and being photo-initiator-free, including the step of maintaining a substantially inert atmosphere in the curing zone where the substrate is exposed to said ultra-violet light.
The preferred multi-functional materials have a functionality of at least three.
Preferably, the inert atmosphere is obtained by purging the curing zone with inert gas such as nitrogen.
Advantageously, the oxygen concentration in the curing zone is less than 1,000 ppm and preferably less than 100 ppm.
Preferably, the multi-functional material comprises one or more reactive diluents.
Conveniently, the multi-functional material comprises one or more materials, each material having a molecular weight in excess of 480.
Advantageously, the multi-functional material comprises one or more materials which have three or more functional acrylate groups.
Conveniently, the coating material contains a prepolymer, and may comprise polyester acrylate, polyurethane acrylate, epoxyacrylate or a full acrylic material.
Conveniently, the pre-polymer is multi-functional.
Advantageously, the coating composition comprises, in addition to the reactive part, a filler, and the filler may comprises clay, silica or magnetisable particles.
Preferably, the power output of the lamp is at least 180 watts/cm and may be substantially 240 watts/cm.
Conveniently, W light from the lamp has a substantial spectral content in the range 200-300 nm.
Preferably, W light from the lamp has additional spectral content with peaks of approximately 370 nm, 408 nm and 438 nm.
Two or more lamps may be provided in the curing zone.
The lamps may have different spectral properties or may have substantially identical spectral properties.
The invention relates to a substrate when coated by a method as described above.
In order that the invention may be more readily understood, and so that further features thereof may be appreciated, the invention will now be described, by way of example, with reference to the accompanying drawings in which:
FIGURE 1 is a diagrammatic view of an apparatus for use in curing a coating on a substrate;
FIGURE 2 is a graphical indication of the spectral output of a preferred W lamp;
FIGURE 3 is a graphical representation of the spectral output of an alternative preferred W lamp; and
FIGURE 4 shows the chemical structure of a reactant.
Referring initially to Figure 1 of the accompanying drawings, an apparatus for curing a coating applied to a substrate is illustrated.
An apparatus is illustrated which comprises a pair of rollers 1,2 adapted to guide a substrate 3, such as a sheet of aluminium foil or a sheet of paper, through the illustrated apparatus. The substrate 3 is coated, before entering the apparatus, completely or partially, with a curable composition which will be described in greater detail hereinafter. The curable composition may be applied as an un-broken coating or may be applied in the form of printing.
The rollers 1,2 guide the substrate 3 through a channel 4 defined between a cooled backing plate 5, and a super-imposed cover 6. The cover 6 supports two lamps 7,8.
The lamp 7 can be a "D" lamp, as supplied by Fusion Inc.
The lamp 7 is located above a quartz window 9 that is sealed against the cover 6 so that light from the lamp 7 may shine through the quartz window 9 on to the substrate 3 as it passes through a curing zone formed by the channel 4.
The lamp 8 can be a "H" lamp as supplied by Fusion
Inc. and is also associated with a quartz window 10 which is formed integrally with the cover 6 so that light from the lamp 8 can pass through the quartz window 10 into the curing zone in channel 4, and thus on to the substrate 3.
The lamps 7,8 each have a focussing reflector. The position of the lamps may be interchanged. In an alternative embodiment, only one lamp may be used, or two lamps of the same type may be used.
The lamps 7 and 8 emit W light with wavelengths in the band 200 to 550 mm. The light is directed on to the substrate in a region in the central part of the channel 4.
The channel 4 is flushed with nitrogen in order to ensure that there is an inert atmosphere having a minimum quantity of oxygen within the channel. Thus, nitrogen is introduced through an inlet conduit 11 and passes to a dispersing nozzle 12 known as the "inlet knife" which is located on the under-side of the cover 6 above the roller 1, and which is adapted to prevent oxygen entering the channel 4. The nitrogen flows along the channel 4, past the region where the W light is directed on to the substrate, in the same direction as the direction of movement of the substrate 3. Nitrogen may also be injected into the channel 4 via nozzles located around the periphery of each quartz window. At the end of the channel 4 adjacent the roller 2 nitrogen flowing through a conduit 13 is passed through a nozzle 14 on the underside of the cover into the channel 4. Thus, there is a continuous flow of nitrogen within the channel 4 such that the concentration of oxygen within the channel 4 is less than 1,000 ppm and preferably less than 100 ppm. Instead of using nitrogen, other inert gases could be used. However, nitrogen is preferred because it is the least expensive inert gas.
The lamps 7 and 8 are supplied in a modular form, each module is 25.4 mm wide and extends transversely across the direction of movement of the web 3 through the channel 4.
The lamps are high intensity lamps using medium pressure mercury vapour bulbs operating at a power level in excess of 140 watts per linear centimetre, preferably in excess of 180 watts per linear centimetre, and most preferably in the region of 240 watts per linear centimetre.
The output spectrum of the "D" lamp 7 is illustrated in Figure 2. It can be observed that the spectrum has a substantial spectral content within the range of 350-450 nm, with specific peaks at 355, 370, 383 and 408 nm. There is spectral content in the region of 200-350 nm, although the spectral content in the 200-250 nm range is minimal.
The spectrum of the "H" lamp 8 is illustrated in
Figure 3. It can be seen that the spectrum has substantial spectral content in the region of 200-300 nm, with the spectral content at the longer wavelengths being restricted to isolated peaks at 312 nm, 370 nm, 408 nm and 438 nm.
The spectral content in the region of 200-300 nm comprises a very broad peak centred on 225 nm and spanning the area from 210-240 nm and a further relatively broad peak, which is less clearly defined, but which is substantially centred on 262 nm and effectively spans the range of 240-280 nm.
It is believed that this very substantial spectral content at these very short wavelengths plays a significant role in creating free radicals to initiate polymerisation. The very high energy present in the well defined peaks at higher frequencies may also contribute.
The reactive part of the curable coating that is applied to the web 3 does not contain a photo-initiator, but does contain a substantial proportion (between 30% and 100% by weight) of multi-functional radiation curable elements. A multi-functional radiation curable element is a radiation curable element which comprises two or more functional groups. Functional groups are acrylate groups with C=C double bonds. If functionality is expressed as a number, the number indicates the number of C=C double bonds available to react, present in acrylate groups.
The radiation curable elements are preferably of low viscosity and can be considered to be reactive diluents, not only providing reactive capabilities, but also maintaining, in the unreacted state, the desired liquid properties of the coating material.
It is preferred that the average molecular weight of any single multi-functional radiation curable element utilised in the curable coating should be greater than 480.
It has been found that relatively low molecular weight radiation curable elements may give rise to skin irritation. It is, however, believed that by utilising a molecular weight greater than 480, the risk of skin irritation arising is substantially reduced or obviated.
Typical examples of multi-functional radiation curable reactive diluents are propoxylated pentaerythritol tetraacrylate or ethoxylated pentaerythritol tetra-acrylate. An alternative material comprises "OTA 480", a triacrylated low viscosity material available from UCB Chemicals of
Anderlecht Str. 33, B-1620 Drogenbos, Belgium. The structure of OTA 480 is shown in Figure 4.
The curable coating may optionally comprise, in addition to the reactive part, a non-reactive part or filler that may comprise clay or silica. In some cases, where the coating is to have magnetic properties, the filler may comprise metal particles that may be magnetised.
It is believed that the very high intensity W radiation applied by the lamps to the curable material generates sufficient free radicals to initiate the curing of the coating.
As the reaction takes place within the substantially inert atmosphere, it is thought that even though a relatively low number of radicals may be produced, because of the high functionality of the coating material, and because the radicals are not subject to oxygen quenching, the radicals that are available to initiate the reaction are sufficient to enable the reaction to proceed very rapidly. Although multi-functional materials, where functionality is greater than 3, are highly reactive, they are believed to undergo a relatively low level of conversion to form a fully cured coating, when compared to mono or di-functional materials.
It is believed that the physical properties of a coating formed solely from multi-functional reactive diluents of low viscosity, whilst sufficient for many purposes, may not be considered sufficient for use as a high performance coating. In order to produce a coating formulation that exhibits solvent resistance and stain resistance, it has been found appropriate to combine, with the reactive diluents, a pre-polymer which preferably contains some unsaturation. A pre-polymer is a reactive material of relatively high viscosity. A pre-polymer, when used alone, does not exhibit liquid properties that are appropriate for a coating material that could be used for example in a direct gravure coating process. Examples of suitable pre-polymers are polyester acrylates, polyurethane acrylates and epoxy acrylates. The functionality of these materials is normally 2 or 3 but can be up to 6. It is thought that the higher the functionality of the prepolymers, the faster the curing performance of the coating.
EXAMPLE 1
A series of multi-functional materials were coated on to aluminium foil at a coat weight of approximately 10g/m2.
The coated foil was passed through a curing apparatus, similar to that shown in Figure 1, but with only one lamp at a speed of 20 m/min. Initially, the lamp was an "H" lamp, and subsequently the experiment was repeated using a "D" lamp. The lamps were each operated at a power level of 240 watts/centimetre. The cured coating was subsequently tested using an acetone rub test utilising a SATRA rub tester. Such a tester provides an indication of the degree of curing. Solvent resistance is indicated as the number of double rubs effected before the coating applied to the aluminium foil is removed. The greater the number of rubs, the more solvent resistant is the coating.
The results are set out in Table 1.
TABLE 1
Coating Composition Solvent Resistance - Acetone rubs H Bulb D Bulb Tripropan-glycol diacrylate < 2 < 2 OTA 480 triacrylate j 40 | < 2 Tetra-acrylates Ebecryl 40 (UCB) | 95 95 | < 2 Ethoxylated pentaerythritol tetra-acrylate | 45 ! < 2 (Croda) Tetra-acrylate with pre-polymer Actilane 320 PP 50 150 | < 2 Epoxy acrylate with 50% Propoxylated pentaerythritol tetra-acrylate (Ackros) Ebecryl 40 is a tetra-functional acrylated reactive diluent available from UCB Chemicals. The ethoxylated pentaerythritol tetra-acrylate was obtained from Croda
Resins Ltd. of Crabtree Manorway, South Belvedere, Kent
DA17 6BA. Actilane 320 PP 50 is obtained from Ackros
Chemicals, Eccles Site, Bentcliffe Way, P.O. Box 1, Eccles,
Manchester M30 OBH.
Example 1 shows that when the coating composition comprises only a di-acrylate, the solvent resistance has a very low value. When tri-acrylates or tetra-acrylates are utilised, a much greater degree of solvent resistance is achieved. When a tetra-acrylate mixed with a pre-polymer is utilised, there is substantial improvement in the performance of the cured coating. This is believed to be due to the introduction of higher molecular weight epoxy groups in the cross-linked structure of the coating.
EXAMPLE 2
A coating of HH52-0103 02 EBC foil coating material obtained from Glasurit GmbH, Postfach 6123, D-48136
Muenster, Germany, was applied at a coat weight of approximately 10g/m2 to an aluminium foil. This material comprises a relatively small proportion epoxy acrylate and a relatively large proportion of ethoxylated pentaerythritol tetra-acrylate. The coated foil was passed at various speeds through a curing apparatus similar to that shown in Figure 1 but with only a single "H" lamp 7 operating. In an initial series of experiments, the "H" lamp was operated at a power of 240 watts per centimetre and in another series of experiments the "H" lamp was operated at a power of 160 watts per centimetre. The acetone rub test as described with reference to Example 1, was subsequently used to indicate the degree of curing.
The results are shown in Table 2.
TABLE 2
Speed Solvent Resistance Acetone rubs @ 240 W/cm @ 160 W/cm 30 M/min 100 11 40 40 M/min 35 9 50 M/min 9 1 60 M/min 4 1 Example 2 illustrates that the degree of curing of the coating is improved when the coating is provided with a substantial energy input in the W spectrum. The best results are achieved with a relatively low speed of movement of the substrate through the curing apparatus and with the application of very intense high energy light. It can be seen that it is important, for a satisfactory cure to be achieved, for there to be a sufficient power input for a sufficient period of time. The degree of cure achieved does not increase linearly with lower speed of passage through the curing zone (i.e. does not increase linearly with the exposure time to intense UV light). As can be seen, especially at 240 watts per centimetre, the degree of cure achieved increases very substantially, almost exponentially, with increased residence time in the curing zone.
It is believed that an even higher degree of cure can be achieved utilising two lamps within the curing zone.
This is shown in Example 3 where the same coating is applied and cured using two lamps at a much higher speed.
EXAMPLE 3
A coating of HH52-0103 02 EBC foil coating material was coated on to a printed paper (Paper 13-2606), using a gravure coating unit at a coat weight of approximately 8 g/m2 and a run speed of 80 metres per minute. The coated paper was passed through a W curing apparatus of a type illustrated in Figure 1 flushed with nitrogen gas to as to achieve a residual oxygen level within the curing region of less than 100 ppm. The curing zone was illuminated, through quartz windows, by two high intensity W lamps, one "H" bulb and one "D" bulb utilising focus-reflectors to direct W light on to the coating to cure it to form a dry film, the two lamps operating at a power of 240 watts per linear centimetre.
The solvent resistance was greater than 50 acetone rubs (measured as in Example 2).
To test the performance of the coated paper as a furniture surfacing material, a sample of the coated paper was laminated, using aminoplast adhesive, on to a piece of chipboard. Then stain and scratch tests were carried out using the techniques described in ISO 4211. For comparison purposes, the test run was repeated, adding to the coating material the photo-initiator recommended by, and obtainable from, Glasurit GmbH, which is a methyl-phenyl-glyoxylate identified as SR07 641H. This coated paper was also laminated to a piece of chipboard using aminoplast adhesive. For further comparison, a sample of commercially available furniture foil which had been lacquered using a water-based amino polyester lacquer and then thermally cured, was also laminated, using aminoplast adhesive, to chipboard to represent a current commercially acceptable industry performance standard.
The results are given in Table 3, where stain resistance is indicated on a 1-5 scale (5 being the best result and 1 being the worst result).
TABLE 3
ISO 4211 Stain Resistance
Test Liquid Thermal Cured UV No. Photoinitiator UV + 0.5% SRO7-641H Lacquer Acetic Acid 3.0 3.0 2.0 Acetone 3.0 3.0 3.0 Ammonia solution 3.0 3.0 3.0 Blackcurrant juice 3.0 3.0 3.0 Citric acid 3.0 3.0 3.0 Cleansing agent 3.5 3.0 3.0 Coffee 3.0 3.5 3.5 Disinfectant (DETTOL) 3.5 4.0 4.0 Disinfectant (SAVLON) 3.0 4.0 4.0 Endorsing ink 4.0 3.0 3.0 Ethanol 3.5 3.5 3.5 Ethyl/Butyl acetate 3.5 3.5 3.0 Iodine 4.0 3.0 3.0 MIlk (condensed) 3.0 3.0 3.0 Olive Oil 3.5 3.5 3.5 Paraffin oil BP 3.5 3.5 3.0 SBP Spirit 4.0 3.0 3.0 Sodium carbonate 4.0 4.0 4.0 Sodium chloride 4.0 4.0 3.0 Tea 4.0 4.0 3.5 Water 3.5 3.5 3.0 TOTALS: 72.5 71.0 67.0 Example 3 indicates that a coating composition in accordance with the present invention, with no photoinitiator, provides a superior performance to a coating composition which does include a photo-initiator. The performance achieved by the material of the present invention is very similar to the performance achieved by the industry-acceptable-standard utilised for comparison purposes. Furthermore, by utilising a preferred combination of W lamp power, spectrum and reactive materials, the process can operate at higher speeds.
Consequently, it is believed that the present invention provides a method of producing an industryacceptable material without the use of photo-initiators, but whilst still providing the other advantages of W curing.
The coating techniques described above have been found to be particularly suitable for applying coatings to flexible papers or films, such as papers or films produced on high speed coating and printing machines. The coatings have been found to be especially valuable for use on surfaces that are found in the home environment. Thus, the coatings may be applied to surfacing materials intended for application to furniture, walls, floors and ceilings.
However, it is to be understood that the method described above may be utilised for less demanding coating applications, such as varnishes for books, magazines or record sleeves. The method described above may also be utilised for fabricating coated materials for use in packaging where low odour coatings, or coatings which do not impart a "taste" to products, are of particular value.
Claims (24)
- CLAIMS: 1. A method of coating a substrate, the method comprising the steps of applying a coating composition to at least selected areas of the substrate, exposing the coated substrate to ultra-violet light from at least one lamp having a power output of at least 140 watts per linear centimetre in a curing zone, to initiate curing of the coating, the coating composition comprising a mixture including at least a reactive part comprising between 30% and 100% multi-functional material and being photoinitiator-free, including the step of maintaining a substantially inert atmosphere in the curing zone where the substrate is exposed to said ultra-violet light.
- 2. A method according to Claim 1 wherein the inert atmosphere is obtained by purging the said curing zone with inert gas.
- 3. A method according to Claim 2 wherein the inert gas comprises nitrogen.
- 4. A method according to any one of the preceding Claims wherein the oxygen concentration within the said curing zone is less than 1,000 parts per million.
- 5. A method according to Claim 4 wherein the oxygen concentration is less than 100 parts per million.
- 6. A method according to any one of the preceding Claims wherein the multi-functional material comprises one or more reactive diluents.
- 7. A method according to any one of the preceding Claims wherein the multi-functional material comprises one or more materials, the or each material having a molecular weight in excess of 480.
- 8. A method according to any one of the preceding Claims wherein the multi-functional material comprises one or more materials which have three or more functional acrylate groups.
- 9. A method according to Claim 6, 7 or 8 wherein the coating material additionally contains a pre-polymer.
- 10. A method according to Claim 9 wherein the pre-polymer comprises polyester acrylate, polyurethane acrylate, epoxyacrelate, or a full acrylate material.
- 11. A method according to Claim 9 or 10 wherein the prepolymer is multi-functional.
- 12. A method according to any one of the preceding Claims wherein the coating composition comprises, in addition to the reactive part, a filler.
- 13. A method according to Claim 12 wherein the filler is clay.
- 14. A method according to Claim 12 wherein the filler is silica.
- 15. A method according to Claim 12 wherein the filler is magnetisable particles.
- 16. A method according to any one of the preceding Claims wherein the power output of the lamp is at least 180 watts/cm.
- 17. A method according to Claim 16 wherein the power output of the lamp is substantially 240 watts/cm.
- 18. A method according to any one of the preceding Claims wherein W light from the lamp has a substantial spectral content in the range of 200-300 nm.
- 19. A method according to Claim 18 wherein W light from the lamp has a spectral content at peaks of approximately 370 nm, 408 nm and 438 nm.
- 20. A method according to any one of the preceding Claims wherein two lamps are provided in the curing zone, the lamps having different spectral properties.
- 21. A method according to any one of Claims 1 to 19 wherein two lamps are provided in the curing zone, the lamps having substantially identical spectral properties.
- 22. A substrate when coated by a method according to any one of the preceding Claims.
- 23. A method of coating a substrate substantially as herein described by way of example.
- 24. Any novel feature or combination of features disclosed herein.
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9716194A GB2327892B (en) | 1997-07-31 | 1997-07-31 | Improvements in or relating to curable coating |
AU83638/98A AU8363898A (en) | 1997-07-31 | 1998-07-03 | A method of coating a substrate |
US09/463,560 US6808757B1 (en) | 1997-07-31 | 1998-07-03 | Method of coating a substrate |
AT98934030T ATE284434T1 (en) | 1997-07-31 | 1998-07-03 | METHOD FOR COATING A SUBSTRATE |
PCT/SE1998/001309 WO1999006489A1 (en) | 1997-07-31 | 1998-07-03 | A method of coating a substrate |
DE1998628057 DE69828057D1 (en) | 1997-07-31 | 1998-07-03 | PROCESS FOR COATING A SUBSTRATE |
BRPI9811715-7A BR9811715B1 (en) | 1997-07-31 | 1998-07-03 | Method for coating a substrate. |
EP98934030A EP1000125B1 (en) | 1997-07-31 | 1998-07-03 | A method of coating a substrate |
CNB988085186A CN1156540C (en) | 1997-07-31 | 1998-07-03 | A method of coating a substrate |
HK01101228A HK1030233A1 (en) | 1997-07-31 | 2001-02-21 | A method of coating a substrate. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9716194A GB2327892B (en) | 1997-07-31 | 1997-07-31 | Improvements in or relating to curable coating |
Publications (3)
Publication Number | Publication Date |
---|---|
GB9716194D0 GB9716194D0 (en) | 1997-10-08 |
GB2327892A true GB2327892A (en) | 1999-02-10 |
GB2327892B GB2327892B (en) | 2001-11-14 |
Family
ID=10816765
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9716194A Revoked GB2327892B (en) | 1997-07-31 | 1997-07-31 | Improvements in or relating to curable coating |
Country Status (10)
Country | Link |
---|---|
US (1) | US6808757B1 (en) |
EP (1) | EP1000125B1 (en) |
CN (1) | CN1156540C (en) |
AT (1) | ATE284434T1 (en) |
AU (1) | AU8363898A (en) |
BR (1) | BR9811715B1 (en) |
DE (1) | DE69828057D1 (en) |
GB (1) | GB2327892B (en) |
HK (1) | HK1030233A1 (en) |
WO (1) | WO1999006489A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1324835A1 (en) * | 2000-09-18 | 2003-07-09 | Ecolab Inc. | Portable radiation cure device |
WO2003057741A1 (en) * | 2001-12-21 | 2003-07-17 | 3M Innovative Properties Company | Multi-stage irradiation process for producing of acrylic based adhesive |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6720042B2 (en) | 2001-04-18 | 2004-04-13 | 3M Innovative Properties Company | Primed substrates comprising radiation cured ink jetted images |
US6896944B2 (en) | 2001-06-29 | 2005-05-24 | 3M Innovative Properties Company | Imaged articles comprising a substrate having a primed surface |
US6881458B2 (en) | 2002-06-03 | 2005-04-19 | 3M Innovative Properties Company | Ink jet receptive coating |
US7638780B2 (en) * | 2005-06-28 | 2009-12-29 | Eastman Kodak Company | UV cure equipment with combined light path |
CN101045833B (en) * | 2007-04-11 | 2010-09-08 | 江苏工业学院 | Preparation method of modified ultroviolet light solidified wooden articles paint by in-situ method |
US20140001181A1 (en) * | 2012-07-02 | 2014-01-02 | Pramod K. Sharma | UV-Cured Strengthening Coating For Glass Containers |
JP6774012B2 (en) * | 2016-06-28 | 2020-10-21 | ウシオ電機株式会社 | Light irradiation device and photocuring device equipped with this |
JP6774013B2 (en) * | 2016-06-28 | 2020-10-21 | ウシオ電機株式会社 | Light irradiation device and photocuring device equipped with this |
CN110314804B (en) * | 2019-08-16 | 2021-08-24 | 台州锐祥机械设备有限公司 | Polycrystalline silicon chip solidifying device |
CN113634464B (en) * | 2021-05-14 | 2024-05-24 | 邦弗特新材料股份有限公司 | MEC combined light source system for UV paint curing |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1345905A (en) * | 1970-04-22 | 1974-02-06 | Hildebrand Maschinenbau Gmbh R | Method and an apparatus for the hardening of a coating applied to a body |
GB1372374A (en) * | 1970-11-30 | 1974-10-30 | Weyerhaeuser Co | Curing of film by exposure to ultraviolet light |
US3918393A (en) * | 1971-09-10 | 1975-11-11 | Ppg Industries Inc | Method of producing flat (non-glossy) films |
US4143468A (en) * | 1974-04-22 | 1979-03-13 | Novotny Jerome L | Inert atmosphere chamber |
GB1580302A (en) * | 1977-03-04 | 1980-12-03 | Thomson Csf | Compounds crosslinkable by photon irradiation |
GB2098617A (en) * | 1981-03-09 | 1982-11-24 | Fuji Photo Film Co Ltd | Magnetic recording medium |
EP0071948A1 (en) * | 1981-08-03 | 1983-02-16 | Mitsubishi Rayon Co., Ltd. | Method and apparatus for surface-hardening treatment of synthetic resin articles |
EP0086474A1 (en) * | 1982-02-12 | 1983-08-24 | Union Carbide Corporation | Process for producing textured coatings |
EP0096951A2 (en) * | 1982-06-10 | 1983-12-28 | Acumeter Laboratories Inc. | Method of and apparatus for producing adhesive-coated sheet materials usable with radiation-cured silicone release coatings and the like |
GB2127714A (en) * | 1982-09-29 | 1984-04-18 | Armstrong World Ind Inc | Uv curing process and product |
EP0618237A1 (en) * | 1993-03-31 | 1994-10-05 | Fusion Systems Corporation | Polymerization process |
WO1994022596A1 (en) * | 1993-04-01 | 1994-10-13 | Ppg Industries, Inc. | Compositions and methods for producing high gloss radiaton curable coatings |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4557975A (en) | 1983-12-30 | 1985-12-10 | General Electric Company | Photocurable acrylate-acrylonitrile coated plastic articles |
WO1985003670A1 (en) * | 1984-02-21 | 1985-08-29 | Mitsubishi Rayon Co | Heat-resistant resin moldings having excellent abrasion resistance and process for their production |
US4902378A (en) * | 1988-04-27 | 1990-02-20 | Minnesota Mining And Manufacturing Company | Polymer with reduced internal migration |
FR2649111B1 (en) | 1989-06-29 | 1991-09-13 | Poudres & Explosifs Ste Nale | METHOD FOR MANUFACTURING RADIORETICULATING COATINGS, NEW RADIORETICULABLE COMPOSITIONS AND NEW CARBONATES |
US5188900A (en) * | 1989-10-18 | 1993-02-23 | Dow Corning Corporation | Substrates having an abrasion-resistant coating formed thereon |
US5234970A (en) * | 1991-07-16 | 1993-08-10 | W. R. Grace & Co.-Conn. | Dual curing composition based on isocyanate trimer and use thereof |
US5633049A (en) * | 1995-04-20 | 1997-05-27 | Minnesota Mining And Manufacturing Company | Method of making protective coating for thermoplastic transparencies |
DE10035961A1 (en) * | 2000-07-24 | 2002-02-07 | Basf Ag | Process for coating substrates |
-
1997
- 1997-07-31 GB GB9716194A patent/GB2327892B/en not_active Revoked
-
1998
- 1998-07-03 WO PCT/SE1998/001309 patent/WO1999006489A1/en active IP Right Grant
- 1998-07-03 US US09/463,560 patent/US6808757B1/en not_active Expired - Lifetime
- 1998-07-03 AT AT98934030T patent/ATE284434T1/en not_active IP Right Cessation
- 1998-07-03 EP EP98934030A patent/EP1000125B1/en not_active Expired - Lifetime
- 1998-07-03 BR BRPI9811715-7A patent/BR9811715B1/en not_active IP Right Cessation
- 1998-07-03 AU AU83638/98A patent/AU8363898A/en not_active Abandoned
- 1998-07-03 CN CNB988085186A patent/CN1156540C/en not_active Expired - Fee Related
- 1998-07-03 DE DE1998628057 patent/DE69828057D1/en not_active Expired - Lifetime
-
2001
- 2001-02-21 HK HK01101228A patent/HK1030233A1/en not_active IP Right Cessation
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1345905A (en) * | 1970-04-22 | 1974-02-06 | Hildebrand Maschinenbau Gmbh R | Method and an apparatus for the hardening of a coating applied to a body |
GB1372374A (en) * | 1970-11-30 | 1974-10-30 | Weyerhaeuser Co | Curing of film by exposure to ultraviolet light |
US3918393A (en) * | 1971-09-10 | 1975-11-11 | Ppg Industries Inc | Method of producing flat (non-glossy) films |
US4143468A (en) * | 1974-04-22 | 1979-03-13 | Novotny Jerome L | Inert atmosphere chamber |
GB1580302A (en) * | 1977-03-04 | 1980-12-03 | Thomson Csf | Compounds crosslinkable by photon irradiation |
GB2098617A (en) * | 1981-03-09 | 1982-11-24 | Fuji Photo Film Co Ltd | Magnetic recording medium |
EP0071948A1 (en) * | 1981-08-03 | 1983-02-16 | Mitsubishi Rayon Co., Ltd. | Method and apparatus for surface-hardening treatment of synthetic resin articles |
EP0086474A1 (en) * | 1982-02-12 | 1983-08-24 | Union Carbide Corporation | Process for producing textured coatings |
EP0096951A2 (en) * | 1982-06-10 | 1983-12-28 | Acumeter Laboratories Inc. | Method of and apparatus for producing adhesive-coated sheet materials usable with radiation-cured silicone release coatings and the like |
GB2127714A (en) * | 1982-09-29 | 1984-04-18 | Armstrong World Ind Inc | Uv curing process and product |
EP0618237A1 (en) * | 1993-03-31 | 1994-10-05 | Fusion Systems Corporation | Polymerization process |
WO1994022596A1 (en) * | 1993-04-01 | 1994-10-13 | Ppg Industries, Inc. | Compositions and methods for producing high gloss radiaton curable coatings |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1324835A1 (en) * | 2000-09-18 | 2003-07-09 | Ecolab Inc. | Portable radiation cure device |
EP1324835A4 (en) * | 2000-09-18 | 2004-10-27 | Ecolab Inc | Portable radiation cure device |
WO2003057741A1 (en) * | 2001-12-21 | 2003-07-17 | 3M Innovative Properties Company | Multi-stage irradiation process for producing of acrylic based adhesive |
US6866899B2 (en) | 2001-12-21 | 2005-03-15 | 3M Innovative Properties Company | Polymerization method comprising sequential irradiation |
CN1330674C (en) * | 2001-12-21 | 2007-08-08 | 3M创新有限公司 | Multi-stage irradiation process for producing of acrylic based adhesive |
Also Published As
Publication number | Publication date |
---|---|
US6808757B1 (en) | 2004-10-26 |
EP1000125A1 (en) | 2000-05-17 |
ATE284434T1 (en) | 2004-12-15 |
EP1000125B1 (en) | 2004-12-08 |
BR9811715B1 (en) | 2008-11-18 |
GB2327892B (en) | 2001-11-14 |
HK1030233A1 (en) | 2001-04-27 |
GB9716194D0 (en) | 1997-10-08 |
CN1156540C (en) | 2004-07-07 |
CN1268157A (en) | 2000-09-27 |
AU8363898A (en) | 1999-02-22 |
WO1999006489A1 (en) | 1999-02-11 |
DE69828057D1 (en) | 2005-01-13 |
BR9811715A (en) | 2000-08-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0632111B1 (en) | Coating process using radiation curable compositions | |
EP1473341B1 (en) | Inkjet ink relatively free of photoinitiator and method and apparatus of curing the ink. | |
RU2311968C2 (en) | Water-containing coating composition for the methods of transfer of the film and the cast product | |
EP0894029B1 (en) | Method for producing a coating | |
Scherzer et al. | Real-time FTIR–ATR spectroscopy to study the kinetics of ultrafast photopolymerization reactions induced by monochromatic UV light | |
US4309452A (en) | Dual gloss coating and process therefor | |
US6808757B1 (en) | Method of coating a substrate | |
US5629359A (en) | Radiation curable compositions | |
US6080450A (en) | Composition exhibiting improved fluorescent response | |
US3943046A (en) | UV curing process employing flash photolysis | |
RU2311967C2 (en) | Heat-seal coating composition for the methods of transfer of the film and the cast product | |
WO2003037936A1 (en) | Visible-light curable composition | |
US4639472A (en) | N-vinyl-2-oxazolidinones as reactive diluents in actinic radiation curable coatings | |
JP2007209869A (en) | Curing method of photocuring composition, its coating film and base material covered with the coating film | |
KR101446598B1 (en) | Method for coating a uv coating material on a board | |
US6538044B2 (en) | Fragranced lacquer coating and process for preparation thereof to be screen printed | |
JPH11302342A (en) | Active energy ray-curable resin composition and formation of coating film using the same | |
US6277897B1 (en) | Photoinitiators and applications therefor | |
JPH10204327A (en) | Active energy ray-curable resin composition, and method for forming film therefrom | |
JPH023455A (en) | Curing of organic coated article | |
Mehnert | Das8. UV‐Cured Supermatt Surfaces With Low Migration | |
JP2001301305A (en) | Print covering matter and manufacturing method therefor | |
US4774305A (en) | N-vinyl-2-oxazolidinones as reactive diluents in actinic radiation curable coatings | |
Oil and Colour Chemists’ Association et al. | Ultraviolet-Cured Coatings | |
KR20230098198A (en) | coatings and primers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
773K | Patent revoked under sect. 73(2)/1977 |
Free format text: PATENT REVOKED ON 20060125 |